U.S. patent application number 16/082549 was filed with the patent office on 2019-03-07 for multi-layered flame retardant and chemical resistant composites and methods of making and using the same.
The applicant listed for this patent is Precision Fabrics Group, Inc.. Invention is credited to Ladson L. Fraser, Samuel Mark Gillette.
Application Number | 20190070835 16/082549 |
Document ID | / |
Family ID | 59852309 |
Filed Date | 2019-03-07 |
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United States Patent
Application |
20190070835 |
Kind Code |
A1 |
Fraser; Ladson L. ; et
al. |
March 7, 2019 |
MULTI-LAYERED FLAME RETARDANT AND CHEMICAL RESISTANT COMPOSITES AND
METHODS OF MAKING AND USING THE SAME
Abstract
A multi-layered flame retardant and chemical resistant composite
is described along with methods of making and/or using the same.
The composite may be used in protective apparel and/or personal
protective ensembles (PPE). The composite may be an engineered
textile laminate. The composite may meet NFPA 2113 criteria as an
over-garment for NFPA 2112 Flashover protection PPE garments. The
composite may provide optimized protection to primary flashover
rated PPE, where flames are present, and where chemical hazards are
present.
Inventors: |
Fraser; Ladson L.; (High
Point, NC) ; Gillette; Samuel Mark; (Burlington,
NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Precision Fabrics Group, Inc. |
Greensboro |
NC |
US |
|
|
Family ID: |
59852309 |
Appl. No.: |
16/082549 |
Filed: |
March 14, 2017 |
PCT Filed: |
March 14, 2017 |
PCT NO: |
PCT/US17/22251 |
371 Date: |
September 6, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62310328 |
Mar 18, 2016 |
|
|
|
62383030 |
Sep 2, 2016 |
|
|
|
62451156 |
Jan 27, 2017 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 2250/03 20130101;
B32B 2262/0269 20130101; B32B 2307/7265 20130101; B32B 2262/0238
20130101; B32B 27/285 20130101; B32B 2262/0246 20130101; B32B 5/08
20130101; B32B 27/06 20130101; B32B 2260/046 20130101; B32B 2437/04
20130101; B32B 27/20 20130101; B32B 2260/023 20130101; B32B
2307/554 20130101; B32B 2262/062 20130101; B32B 2262/0253 20130101;
B32B 2571/00 20130101; B32B 5/022 20130101; B32B 2255/20 20130101;
B32B 27/36 20130101; B32B 2255/10 20130101; B32B 2270/00 20130101;
B32B 2262/0276 20130101; A41D 31/085 20190201; B32B 7/12 20130101;
B32B 27/16 20130101; B32B 27/306 20130101; B32B 2307/7244 20130101;
B32B 25/14 20130101; B32B 25/16 20130101; B32B 27/32 20130101; B32B
2262/0261 20130101; B32B 2255/02 20130101; A62D 5/00 20130101; B32B
2262/065 20130101; B32B 2307/50 20130101; B32B 2307/718 20130101;
B32B 27/18 20130101; B32B 2262/0215 20130101; B32B 2307/714
20130101; B32B 25/12 20130101; B32B 27/08 20130101; B32B 2260/021
20130101; B32B 2255/26 20130101; B32B 2262/04 20130101; B32B
2307/734 20130101; B32B 2437/02 20130101; B32B 25/18 20130101; B32B
27/288 20130101; B32B 27/40 20130101; B32B 3/085 20130101; B32B
27/281 20130101; A41D 31/10 20190201; B32B 7/14 20130101; B32B
29/02 20130101; B32B 2307/7242 20130101; B32B 27/286 20130101; B32B
27/308 20130101; B32B 2262/106 20130101; B32B 2307/3065 20130101;
B32B 2307/748 20130101; B32B 2437/00 20130101; A62B 17/00 20130101;
B32B 5/26 20130101; B32B 2307/732 20130101; B32B 5/147 20130101;
B32B 27/12 20130101; B32B 2262/02 20130101; B32B 2262/067 20130101;
B32B 25/08 20130101; B32B 2250/05 20130101; B32B 2262/14 20130101;
B32B 2255/24 20130101; B32B 27/304 20130101; B32B 27/34
20130101 |
International
Class: |
B32B 27/12 20060101
B32B027/12; B32B 7/12 20060101 B32B007/12; B32B 5/02 20060101
B32B005/02; B32B 27/08 20060101 B32B027/08; B32B 27/20 20060101
B32B027/20; B32B 27/30 20060101 B32B027/30; B32B 5/08 20060101
B32B005/08 |
Claims
1. A multi-layered composite comprising: a first layer comprising a
nonwoven fabric; a second layer comprising a non-flame retardant
chemical barrier polymeric film; and a third layer comprising a
polymeric film; wherein the first layer is adhered to the second
layer with a first flame retardant adhesive and the second layer is
adhered to the third layer with a second flame retardant
adhesive.
2.-15. (canceled)
16. A multi-layered composite comprising: a first layer comprising
a nonwoven fabric; a second layer comprising a non-flame retardant
chemical barrier polymeric film; and a third layer comprising a
flame retardant coating; wherein the first layer is adhered to the
second layer with a first flame retardant adhesive and the second
layer is adhered to the third layer with a second flame retardant
adhesive.
17.-22. (canceled)
23. A multi-layered composite comprising: a first layer comprising
a nonwoven fabric; a second layer comprising a non-flame retardant
chemical barrier polymeric film; and a third layer comprising a
polymeric film; wherein the first layer is adhered to the second
layer with a first adhesive.
24. The multi-layered composite of claim 23, wherein the first
adhesive is not flame retardant.
25. The multi-layered composite of claim 23, wherein the first
adhesive is flame retardant.
26. The multi-layered composite of claim 23, wherein the second
layer is adhered to the third layer with a second adhesive and the
second adhesive is flame retardant.
27. The multi-layered composite of claim 23, wherein the second
layer is in direct contact with the third layer.
28. The multi-layered composite of claim 23, wherein the first
adhesive is a discontinuous layer between the first layer and the
second layer.
29. The multi-layered composite of claim 23, wherein the nonwoven
fabric comprises a fire retardant additive.
30. The multi-layered composite of claim 23, wherein the nonwoven
fabric comprises cellulosic fibers and synthetic fibers.
31. The multi-layered composite of claim 30, wherein the cellulosic
fibers include woodpulp fibers and the synthetic fibers include
polyester fibers.
32. The multi-layered composite of claim 23, wherein the non-flame
retardant chemical barrier polymeric film includes two or more
layers, optionally wherein there is a space and/or absorbent media
between two of the two or more layers.
33. (canceled)
34. The multi-layered composite of claim 23, wherein the non-flame
retardant chemical barrier polymeric film comprises a coextruded
polyethylene-ethylene vinyl alcohol.
35. The multi-layered composite of claim 23, wherein the third
layer comprises a polyvinyl chloride film.
36. The multi-layered composite of claim 23, wherein the non-flame
retardant chemical barrier polymeric film has a difference in
solubility parameter that is at least about 3.0 (calories per
cm.sup.3).sup.1/2 for at least one chemical listed in ASTM F23
F1001.
37. The multi-layered composite of claim 23, wherein the non-flame
retardant chemical barrier polymeric film comprises two or more
layers and at least one of the two or more layers has a difference
in solubility parameter that is at least about 3.0 (calories per
cm.sup.3).sup.1/2 for at least one chemical listed in ASTM F23
F1001.
38. The multi-layered composite of claim 23, wherein the composite
has a chemical hold out of at least 8 hours in accordance with ASTM
F23 F739 and ISO 6529/EN 14325 Chemical Permeation using at least
one chemical listed in ASTM F23 F1001.
39. The multi-layered composite of claim 23, wherein the composite
passes NFPA 701-2015 Method 1 and/or meets the requirements of NFPA
2113.
40. The multi-layered composite of claim 23, wherein the composite
has at least 12.0 pounds of grab tensile according to INDA IST
110.3-92.
41. A protective garment comprising the composite of claim 23.
42. (canceled)
Description
RELATED APPLICATION INFORMATION
[0001] This application claims the benefit of U.S. Provisional
Patent Application Ser. Nos. 62/310,328, filed Mar. 18, 2016;
62/383,030, filed Sep. 2, 2016; and 62/451,156, filed Jan. 27,
2017, the disclosure of each of which is incorporated herein by
reference in its entirety.
FIELD
[0002] The present invention relates generally to multi-layered
flame retardant and chemical resistant composites and to methods of
making and/or using the same, such as, for example, for use in
protective apparel and/or personal protective ensembles (PPE).
BACKGROUND
[0003] Protective apparel and/or PPEs may be desirable or required
for users in a variety of fields (e.g., government, law
enforcement/first responder agencies, petroleum rigs, refineries,
or various industries requiring NFPA 2112 flashover protection PPE)
in some instances, the protective apparel and/or PPE must meet NFPA
standards. For example, the garment may need to be a primary NFPA
2112 garment, which may particularly be needed in law enforcement
or in other first responder situations where longer duration
protection to chemical splash hazards, and associated flame hazards
are common.
SUMMARY OF EXAMPLE EMBODIMENTS
[0004] One aspect of the present invention includes a multi-layered
composite comprising: a first layer comprising a nonwoven fabric; a
second layer comprising a non-flame retardant chemical barrier
polymeric film; and a third layer comprising a polymeric film;
wherein the first layer is adhered to the second layer with a first
flame retardant adhesive and the second layer is adhered to the
third layer with a second flame retardant adhesive. In some
embodiments, the composite may be a laminate. The non-flame
retardant chemical barrier polymeric film provides an excellent
chemical barrier that may have flame resistant properties, but does
not comprise a flame retardant additive within the chemical barrier
polymeric film.
[0005] Another aspect of the present invention includes a
multi-layered composite comprising: a first layer comprising a
nonwoven fabric; a second layer comprising a non-flame retardant
chemical barrier polymeric film; and a third layer comprising a
polymeric film; wherein the first layer is adhered to the second
layer with a first adhesive. In some embodiments, the first
adhesive is not a flame retardant adhesive. In some embodiments,
the first adhesive is a flame retardant adhesive. In some
embodiments, no adhesive is between the second layer and third
layer and a surface of the second layer directly contacts a surface
of the third layer. In some embodiments, the third layer is applied
as a polymeric coating onto a surface of the second layer to form
the polymeric film on the second layer. In some embodiments, the
composite may be a laminate.
[0006] A further aspect of the present invention includes a
composite that passes NFPA 701-2015 Method 1 and/or meets the
requirements of NFPA 2113. In some embodiments, the composite has
at least 12.0 pounds of grab tensile according to INDA IST
110.3-92
[0007] In some embodiments, the composite has a chemical hold out
of at least 8 hours in accordance with ASTM F23 F739 and ISO
6529/EN 14325 Chemical Permeation using at least one chemical in
ASTM F23 F1001 list.
[0008] Another aspect of the present invention includes a
multi-layered composite comprising: a first layer comprising a
nonwoven fabric; a second layer comprising a non-flame retardant
chemical barrier polymeric film; and a third layer comprising a
flame retardant coating; wherein the first layer is adhered to the
second layer with a first flame retardant adhesive and the second
layer is adhered to the third layer with a second flame retardant
adhesive.
[0009] A further aspect of the present invention includes use of a
composite of the present invention in a protective garment (e.g.,
protective apparel and/or PPE).
[0010] Another aspect of the present invention includes a method of
preparing a composite of the present invention.
[0011] The foregoing and other aspects of the present invention
will now be described in more detail including other embodiments
described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 illustrates a composite according to example
embodiments of the present invention.
[0013] FIG. 2 illustrates a further composite according to example
embodiments of the present invention.
[0014] FIG. 3 illustrates an example composite according to example
embodiments of the present invention.
[0015] FIG. 4 illustrates a further example composite according to
example embodiments of the present invention.
[0016] FIG. 5 illustrates a 2 Mil Coextruded 7 layer
Polyethylene/EVOH/Polyethylene film composite according to example
embodiments of the present invention.
DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS
[0017] The present invention will now be described more fully
hereinafter. This invention may, however, be embodied in different
forms and should not be construed as limited to the embodiments set
forth herein. Rather, these embodiments are provided so that this
disclosure will be thorough and complete, and will fully convey the
scope of the invention to those skilled in the art.
[0018] The terminology used in the description of the invention
herein is for the purpose of describing particular embodiments only
and is not intended to be limiting of the invention. As used in the
description of the invention and the appended claims, the singular
forms "a", "an" and "the" are intended to include the plural forms
as well, unless the context clearly indicates otherwise.
[0019] Unless otherwise defined, all terms (including technical and
scientific terms) used herein have the same meaning as commonly
understood by one of ordinary skill in the art to which this
invention belongs. It will be further understood that terms, such
as those defined in commonly used dictionaries, should be
interpreted as having a meaning that is consistent with their
meaning in the context of the present application and relevant art
and should not be interpreted in an idealized or overly formal
sense unless expressly so defined herein. The terminology used in
the description of the invention herein is for the purpose of
describing particular embodiments only and is not intended to be
limiting of the invention. All publications, patent applications,
patents and other references mentioned herein are incorporated by
reference in their entirety. In case of a conflict in terminology,
the present specification is controlling.
[0020] Also as used herein, "and/or" refers to and encompasses any
and all possible combinations of one or more of the associated
listed items, as well as the lack of combinations when interpreted
in the alternative ("or").
[0021] Unless the context indicates otherwise, it is specifically
intended that the various features of the invention described
herein can be used in any combination. Moreover, the present
invention also contemplates that in some embodiments of the
invention, any feature or combination of features set forth herein
can be excluded or omitted. To illustrate, if the specification
states that a complex comprises components A, B and C, it is
specifically intended that any of A, B or C, or a combination
thereof, can be omitted and disclaimed.
[0022] As used herein, the transitional phrase "consisting
essentially of" (and grammatical variants) is to be interpreted as
encompassing the recited materials or steps "and those that do not
materially affect the basic and novel characteristic(s)" of the
claimed invention. See, In re Herz, 537 F.2d 549, 551-52, 190
U.S.P.Q. 461, 463 (CCPA 1976) (emphasis in the original); see also
MPEP .sctn. 2111.03. Thus, the term "consisting essentially of" as
used herein should not be interpreted as equivalent to
"comprising."
[0023] The term "about," as used herein when referring to a
measurable value such as an amount or concentration and the like,
is meant to encompass variations of .+-.10%, .+-.5%, .+-.1%,
.+-.0.5%, or even .+-.0.1% of the specified value as well as the
specified value. For example, "about X" where X is the measurable
value, is meant to include X as well as variations of .+-.10%,
.+-.5%, .+-.1%, .+-.0.5%, or even .+-.0.1% of X. A range provided
herein for a measurable value may include any other range and/or
individual value therein.
[0024] As used herein, the term "osy" refers to weight per area
unit in ounces per square yard.
[0025] As used herein, the term "gsm" refers to weight per area
unit in grams per square meter.
[0026] As used herein, the term "mil" refers to a thickness in
1/1000 inches.
[0027] As used herein, "flame resistant" in reference to a
composite, film, layer, and/or fabric refers to the ability of the
composite, layer, and/or fabric to pass at least one flame
resistance test set forth by the National Fire Protection
Association in "NFPA 701 Standard Methods of Fire Tests for
Flame-Resistant Textiles and Films," 2015 Method 1, 1 st Ed. and
"NFPA 701 Standard Methods of Fire Tests for Flame-Resistant
Textiles and Films," 1989 Small Scale Ed. The entire contents of
each of these NFPA publications is incorporated herein by reference
in their entirety.
[0028] For purposes of this invention, a flame retardant is a
non-polymeric additive or blend of additives used to impart or
increase flame resistance properties of an article or material.
[0029] For purposes of this invention, a flame retardant composite,
film, fabric, and/or layer refers to a composite, film, fabric,
and/or layer that comprises a flame retardant. A flame retardant
composite, film, fabric, and/or layer of the present invention
passes at least one flame resistance test set forth by the National
Fire Protection Association in "NFPA 701 Standard Methods of Fire
Tests for Flame-Resistant Textiles and Films," 2015 Method 1, 1st
Ed. and "NFPA 701 Standard Methods of Fire Tests for
Flame-Resistant Textiles and Films," 1989 Small Scale Ed. A
composite, film, fabric, and/or layer of the present invention may
incorporate a flame retardant within the composite, film, fabric,
and/or layer and/or on a surface of the composite, film, fabric,
and/or layer. In some embodiments, a composite, film, fabric,
and/or layer comprises a flame retardant in an amount sufficient
such that the composite, film, fabric, and/or layer passes at least
one flame resistance test set forth by the National Fire Protection
Association in "NFPA 701 Standard Methods of Fire Tests for
Flame-Resistant Textiles and Films," 2015 Method 1, 1st Ed. and
"NFPA 701 Standard Methods of Fire Tests for Flame-Resistant
Textiles and Films," 1989 Small Scale Ed.
[0030] Provided herein is a composite that includes multiple
different layers. A composite of the present invention may include
at least two layers. In some embodiments, a composite of the
present invention includes at least three layers. For purposes of
this invention, the side of a composite and/or garment that may
face a user is referred to herein as the inner layer. The side of a
composite and/or garment that may face away from the user is
referred to herein as the outer layer.
[0031] For example, as shown in FIG. 1, a composite 100 of the
present invention may comprise a first layer 10, a second layer 20,
and a third layer 30. The first layer 10 of composite 100 may
comprise a nonwoven fabric, as described herein, which may char
when burned and/or exposed to heat and/or flame. The first layer 10
may include a surface 12 that is the inner layer of the composite
100. The second layer 20 may be a non-flame retardant chemical
barrier film, as described herein, which may be engineered and/or
selected to meet the chemical holdout requirements in accordance
with ASTM F23 F739 test procedure and the ASTM F23 F1001 chemical
insult list. The second layer 20 may be adhered to the third layer
30, which may comprise a film (e.g., a flame retardant film or a
non-flame retardant film), as described herein. The third layer 30
may include a surface 14 that is the outer layer of the composite
100. The first layer 10, second layer 20, and third layer 30 may
each be adhesively bonded to an adjoining layer using an adhesive
(e.g., a flame retardant adhesive), as described herein.
[0032] In some embodiments, a composite of the present invention
may be resistant to ASTM F-1001 chemicals in liquid and/or vapor
form and may be flame resistant. In some embodiments, the composite
may be impervious to water and/or dry particles.
[0033] In some embodiments, the composite may comprise and/or may
be a laminate. The composite may be referred to herein as a
"laminated composite". The composite may have a basis weight in a
range of about 0.5 ounces per square yard (osy) to about 14 osy,
such as, for example, about 5 osy to about 10 osy or about 1 osy to
about 8 osy. In some embodiments, the composite may have a basis
weight of about 0.5, 1, 1.5 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5,
or 10 osy. The composite may have a thickness in a range of about
0.001 to about 0.5 inches, such as, for example about 0.005 to
about 0.05 inches.
[0034] The first layer of a composite of the present invention may
comprise a nonwoven fabric comprising a fire retardant additive. In
some embodiments, the fire retardant additive may be applied to at
least one surface of the nonwoven fabric. The nonwoven fabric may
comprise natural fibers (e.g., cellulosic fibers) and/or synthetic
fibers. In some embodiments, one side of the nonwoven fabric may
comprise natural fibers (e.g., cellulosic fibers) and the other
side of the nonwoven fabric may comprise synthetic fibers.
Synthetic fibers and natural fibers may be present in a ratio of
about 5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, or 1:5 (synthetic
fibers:natural fibers). In some embodiments, the ratio of synthetic
fibers to natural fibers is in a range of about 1:1 to about 1:1.5.
The first layer of a composite of the present invention may have a
basis weight in a range of about 1 osy to about 4 osy. In some
embodiments, the first layer may have a basis weight of about 1,
1.5, 2, 2.5, 3, 3.5, or 4 osy. In some embodiments, the first layer
of a composite of the present invention may make up about 8% to
about 50% by weight of the composite, such as, for example, about
20% to about 35%, about 25% to about 45%, or about 15% to about 40%
by weight of the composite.
[0035] Example nonwoven fabrics that may be used in the first layer
of a composite of the present invention include, but are not
limited to, spunlace fabrics, spunbond fabrics, spunbond-containing
fabrics, spinlace fabrics, resin bonded fabrics, thermal bonded
fabrics, air-laid pulp fabrics, stitchbonded fabrics, needlepunch
fabrics, and/or other possible engineered materials maintaining
preferred physical integrity and synergism for final attributes
desired, such as, for example, as described in the Definition of
Nonwovens prescribed by INDA.org. In some embodiments, the nonwoven
fabric is a spunlace fabric. The nonwoven fabric (e.g., a spunlace
fabric) may be made and/or prepared from a combination of
cellulosic and synthetic fibers. Example cellulosic fibers that may
be used to form a nonwoven fabric (e.g., spunlace fabric) include,
but are not limited to, woodpulp fibers, cotton fibers, regenerated
cellulose fibers such as rayon and/or lycocell fibers, cellulose
acetate fibers, cellulose triacetate fibers, jute, hemp, and/or any
bast, leaf, or stem fibers, in some embodiments, the first layer
comprises woodpulp fibers.
[0036] Synthetic fibers that may be used to form the nonwoven
(e.g., spunlace) fabric include, but are not limited to, polyester,
nylon, polypropylene, polylactic acid (PLA) fibers, acrylic fibers,
and/or any other applicable available textile staple fiber that
produces desired attributes, and/or fits a nonwoven (e.g.,
spunlace) process. In some embodiments, the first layer comprises
polyester fibers.
[0037] In some embodiments, the first layer comprises a fiber that
is treated with a flame retardant additive and the fiber is
selected from polyester, nylon, acrylic, acrylonitrile, olyolefin,
vinylidene chloride (saran), cellulose (e.g., acetate, rayon,
lyocell, woodpulp, cotton and/or other natural organic fibers),
silica-containing rayon, melamine (basofil), aramid/paraaramid
(e.g., kevlar, nomex), sulfar, polyethylene, olefin, PEU (e.g.,
spandex), silicone, fluorocarbon, polybenzimidazole (PBI), and/or
carbon fibers.
[0038] In some embodiments, when the nonwoven layer comprises
synthetic fibers and cellulosic fibers, the cellulosic and
synthetic fibers may be in the form of flat layers. For example, a
nonwoven layer may comprise two or more layers (e.g., 2, 3, 4 or
more layers, also referred to herein as sublayers) each of which
may comprise cellulosic fibers and/or synthetic fibers in any
orientation or order. Referring to FIG. 2, composite 150 may
comprise a first layer 10 comprising a nonwoven layer that
comprises two layers 10a, 10b, and one layer may comprise
cellulosic fibers and the other layer may comprise synthetic
fibers. In some embodiments, nonwoven layer 10a (i.e., the nonwoven
layer closest to the second layer 20) may comprise cellulosic
fibers (e.g., woodpulp fibers) and nonwoven layer 10b may comprise
synthetic fibers (e.g., polyester fibers). In some embodiments,
nonwoven layer 10b is the inner layer that faces towards a
user.
[0039] In some embodiments, when the nonwoven layer comprises
synthetic fibers and cellulosic fibers, the cellulosic fibers may
be in the form of sheets of paper and the synthetic fibers may be
in the form of air-laid or carded webs of staple fibers or a
nonwoven sheet of substantially continuous filaments. The webs or
sheets may be bonded or non-bonded. In some embodiments, the weight
ratio of the cellulosic fibers to synthetic fibers in a first layer
of a composite of the present invention may range from 75:25 to
25:75, and in some embodiments from 65:35 to 50:50.
[0040] The weight of the nonwoven fabric (e.g., spun-lace fabric)
used in a composite of the present invention may be selected by the
degree of dimensional stability needed and/or desired as well as
wear durability needed or desired for a particular application
(e.g., for protective apparel applications). In some embodiments, a
weight range for the nonwoven fabric (e.g., spunlace fabric) may be
about 1.0 osy to about 4.0 osy. An example spunlace
woodpulp/polyester fabric that may be used in a composite of the
present invention is commercially available from Jacob Holm
Industries under the tradename Sontara.RTM..
[0041] In some embodiments, the nonwoven fabric may be formed by a
spunlacing process. Example spunlace processes are known in the
art. For example, a pulp containing cellulosic sheet may be applied
to one side of a batt of carded synthetic fibers. The material may
then be passed under a plurality of water jets, which entangle the
synthetic and cellulosic fibers to form a fabric. Methods of making
spunlace fabrics are described in U.S. Pat. No. 4,442,161, the
entire contents of which is incorporated herein by reference in its
entirety.
[0042] A fire retardant additive may be applied to at least one
surface of the nonwoven fabric (e.g., spunlace fabric) at a dry
solids add-on ranging from about 5 to about 45 percent by weight of
the nonwoven fabric. In some embodiments, the dry solids add-on
ranges from about 15 to about 25 percent by weight of the nonwoven
fabric. Any suitable inorganic and/or organic fire retardant
additive may be used. Example inorganic fire retardant additives,
include, but are not limited to, ammonium polyphosphates, ammonium
dihydrogen phosphate, antimony trioxide, sodium antimonate, zinc
borate, zirconium oxides, diammonium phosphate, sulfamic acid,
salts of sulfamic acid, boric acid, salts of boric acid, and/or
hydrated alumina.
[0043] Example organic fire retardant additives that may be used
include, but are not limited to, urea polyammonium phosphate,
chlorinated paraffins, tetrabromobisphenol-A and oligomers thereof,
decabromodiphenyl oxide, hexabromodiphenyl oxide,
pentabromodiphenyl oxide, pentabromotoluene,
pentabromoethylbenzene, hexabromobenzene, pentabromophenol,
tribromophenol derivatives, perchloropentanecyclodecane,
hexabromocyclodecone, tris(2,3-dibromopropyl-1)isocyanurate,
tetrabromobisphenol-S and derivatives thereof,
1,2-bis(2,3,4,5,6-pentabromophenoxy)ethane,
1,2-bis-(2,4,6-tribromophenoxy)ethane, brominated styrene
oligomers, 2,2-bis-(4(2,3-dibromopropyl)3,5-dibromophenoxy)propane,
tetrachlorophthalic anhydride, and/or tetrabromophthalic
anhydride.
[0044] In some embodiments, a combination of fire retardant
additives (e.g., inorganic and/or organic) may be used. In some
embodiments, a nonwoven fabric may comprise a fire retardant
additive that comprises a phosphate, such as, e.g., Spartan 880 FR
sold by Spartan Flame Retardants, Inc. The fire retardant additive
may be applied to the nonwoven fabric by any conventional method
such as, e.g., spraying, contacting the spunlace fabric with a
saturation pad or saturation roller, a dip/nip saturation process,
gravure coating, kiss coating, and/or the like.
[0045] The nonwoven fabric, either before and/or after it is
treated with a fire retardant additive, may be laminated to another
layer of a composite of the present invention. Referring again to
FIG. 1, the first layer 10 comprising the nonwoven fabric may be
adhered to the second layer 20 with an adhesive (e.g., a flame
retardant adhesive). In some embodiments, the adhesive adhering the
first layer 10 to the second layer 20 is not a flame retardant
adhesive. The second layer 20 of the composite 100 may comprise a
non-flame retardant chemical barrier polymeric film (i.e., the
chemical barrier polymeric film is unfilled with a flame retardant
additive). Thus, the non-flame retardant chemical barrier polymeric
film does not comprise a flame retardant additive within the
chemical barrier polymeric film. In some embodiments, a surface of
the non-flame retardant chemical barrier polymeric film and/or
second layer of a composite of the present invention may be in
contact with a flame retardant additive that is part of another
layer of the composite (e.g., the first layer or a flame retardant
adhesive), but a flame retardant additive is not within the
non-flame retardant chemical barrier polymeric film and/or second
layer.
[0046] In some embodiments, the second layer 20 may comprise 1, 2,
3, 4, 5, 6, 7, 8, 9, 10, or more layers, and when there are two or
more layers, each layer may comprise the same material or a
different material than another layer. For example, as shown in
FIG. 2, in some embodiments, the second layer 20 may comprise one
or more layers 20a-20e that may be the same or a different material
compared to another layer of the second layer 20.
[0047] For the non-flame retardant chemical barrier polymeric film
of a composite of the present invention, the primary criterion for
selection of this layer may be its chemical barrier properties.
Secondary criteria for selection of the non-flame retardant
chemical barrier polymeric film may include, e.g., basis weight,
handle-o-meter, thickness, cost and/or flame resistant properties,
which may be subordinated to achieve the chemical barrier
properties of this layer. The non-flame retardant chemical barrier
polymeric film of a composite of the present invention may have a
basis weight in a range of about 0.25 osy to about 3 osy. In some
embodiments, the non-flame retardant chemical barrier polymeric
film may have a basis weight of about 0.25, 0.5, 0.75, 1, 1.25,
1.5, 1.75, 2, 2.25, 2.5, 2.75, or 3 osy. In some embodiments, the
non-flame retardant chemical barrier polymeric film of a composite
of the present invention may make up about 7.5% to about 45% by
weight of the composite, such as, for example, about 10% to about
35% or about 15% to about 25% by weight of the composite.
[0048] The non-flame retardant chemical barrier polymeric film of a
composite of the present invention may serve as a barrier against
liquids, solids, and/or gases. The non-flame retardant chemical
barrier polymeric film may be referred to herein as the second
layer of the composite and may be a chemical barrier layer. The
non-flame retardant chemical barrier polymeric film may by itself
have some degree of flame resistance. Flame resistance may be
measured by flame testing and/or by determining the limiting oxygen
index. For example, the non-flame retardant chemical barrier
polymeric film may by itself have some degree of flame resistance
if the non-flame retardant chemical barrier polymeric film
comprises barrier polymers that have a Limiting Oxygen Index (LOI)
greater than 27 as measured by ASTM D7348-13 and similar methods.
In some embodiments, a flame retardant is incorporated with a
polymer to reduce the tendency for combustion. In some embodiments,
the innate properties of a polymer make it resistant to
combustion.
[0049] In some embodiments, the non-flame retardant chemical
barrier polymeric film of a composite of the present invention may
be a continuous iayer. The non-flame retardant chemical barrier
polymeric film may not comprise any or may have minimal open pores
and/or holes within the film. Discontinuities in the non-flame
retardant chemical barrier polymeric film, such as, for example,
open pores and/or holes, are not desired as they may allow the
insult chemical/permeant to migrate through the non-flame retardant
chemical barrier polymeric film. A continuous non-flame retardant
chemical barrier polymeric film and/or layer thereof may be
achieved by methods known to those of skill in the art including,
but not limited to, extruding a film of a polymer, blowing a film
of a polymer, and/or applying or printing a polymer in a pattern of
discreet points and providing a method for the individual points to
coalesce together such as, e.g., using a solvent, heat, etc.
[0050] The non-flame retardant chemical barrier film may comprise 2
or more layers (e.g., 2, 3, 4, 5, 6, 7, 8, or more), which may be
chosen to prevent the passage of chemicals. In some embodiments,
the non-flame retardant chemical barrier film comprises at least
three layers. In some embodiments, the non-flame retardant chemical
barrier film may comprise at least two layers (e.g., 2, 3, 4, 5, 6,
7, 8, or more) and the at least two layers may be contiguous and/or
continuous.
[0051] In some embodiments, the effectiveness of the non-flame
retardant chemical barrier film in preventing penetration and/or
permeation of chemicals (e.g., liquid and/or gaseous) and/or
biological hazards may be improved by introducing spaces and/or
absorbent media between two or more layers of the non-flame
retardant chemical barrier film. For example, as shown in FIG. 3, a
space and/or absorbent media (e.g., a fabric) 50 may be positioned
between a first layer 20a of the non-flame retardant chemical
barrier film 20 and a second layer 20b of the non-flame retardant
chemical barrier film 20. The space and/or absorbent media may
create a reservoir, which may take up a liquid and/or gas, and/or
the space and/or absorbent media may reduce the pressure gradient.
In some embodiments, the space and/or absorbent media may create an
insulation effect. In some embodiments, including a space and/or
absorbent media between two or more layers of the non-flame
retardant chemical barrier film 20 may create a tortuous path for a
chemical (e.g., liquid and/or gaseous) and/or biological hazard.
The space and/or absorbent media may be discontinuous as shown, for
example, in FIG. 4. As shown in FIG. 4, portions of the first layer
20a and the second layer 20b of the non-flame retardant chemical
barrier film 20 are contiguous, while other portions are
noncontiguous as a space and/or absorbent media 50 is between a
portion of the first layer 20a and the second layer 20b of the
non-flame retardant chemical barrier film 20. Spaces and/or
absorbent media may be arranged in a symmetrical pattern or
asymmetrical pattern (e.g., be randomly distributed). For example,
referring to FIG. 4, an adhesive may be arranged in a symmetrical
or asymmetrical pattern between the first layer 20a and the second
layer 20b of the non-flame retardant chemical barrier film 20, and
the contiguous portions of the first layer 20a and the second layer
20b may be bound together using the adhesive. In some embodiments,
the noncontiguous portions may be areas where the adhesive is not
present or applied so that a space 50 is provided.
[0052] The chemical resistance of the non-flame retardant chemical
barrier film may be enhanced by alternating several types of
polymer layers within the film and/or by adding additional layers
of film. In some embodiments, additional polyethylene layers may be
added to the non-flame retardant chemical film to enhance
protection against polar solvents. Other layers may include, but
are not limited to, ethylene vinyl alcohol (EVOH), nylon (e.g.,
nylon 6 and/or nylon 6,6), polyolefins (e.g., polypropylene (PP)),
polyethylene (PE) (e.g., polyethylene high density and/or
polyethylene low density), polyvinylidene chloride (PVDC) (e.g.,
Saranex.RTM.), polyvinylfluoride (PVF) (e.g., Tedlar.RTM.),
acrylic, acrylonitrile rubber, butyl rubber, chlorosulfonated
polyethylene (e.g., Hypalon.RTM.), ethylene chlorotrifluoroethylene
copolymer (ECTFE) (e.g., Halar.RTM.), ethylene propylene diene
monomer (M-class) rubber-coatings (EPDM rubber), fluorinated
ethylene propylene (FEP), fluoro-elastomer polymers (e.g.,
Viton.RTM.), liquid crystal polymers, metal foils, natural rubber,
neoprene, perfluoroalkoxy copolymer (e.g., Teflon.RTM. PFA),
polimide, polyamide-imide (e.g., Tecator.RTM. and Torlon.RTM.),
polyamides, polesters (e.g., Mylar.RTM.), polyether sulfone,
polyetheretherketone (PEEK, e.g., Victrex.RTM.), polyetherimide,
polymeric coatings, polyphenylsulfone (PPS), polysulfone,
polytetrafluoroethylene (PTFE) (e.g., Teflon.RTM.), polyurethane,
polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF) (e.g.,
Kynar.RTM.) poylvinyl choride-acetate (PCA), styrene butadiene
rubber (SBR), vacuum metallized films, extrudable polymers that are
used for chemical barrier films in the market place, and/or any
variation, combination and/or hybridization thereof. Commercial
examples of chemical barrier films include, but are not limited to,
those that are available from companies such as IsoFlex, Berry
Plastics, Mitsui, Filcon, Kuraray and/or Optimum Plastics. In some
embodiments, the second layer comprises PEEK, polyethylene,
polyolefin, ECTFE, PVF, nylon, EVA, EVOH, polypropylene, polyester,
and/or ethylene-vinyl chloride (EVCL).
[0053] In some embodiments, the layers within the non-flame
retardant chemical barrier film may provide a good barrier to
oxygen and may also provide a good barrier to some solvents, acids
and/or bases. In some embodiments, the incorporation of flame
retardant fillers into a chemical barrier film may reduce the
chemical barrier properties of the film. The non-flame retardant
chemical barrier film may comprise flame-resistant polymers which
may complement properties of the present invention.
[0054] In some embodiments, a component (e.g., polymer) for
preparing and/or forming the non-flame retardant chemical barrier
film may be selected by the component having a low affinity for the
insult chemical(s) of interest (i.e., the chemical(s) for which
protection and/or a barrier against is desired). A composite of the
present invention may comprise a non-flame retardant chemical
barrier film that has a low solubility to the insult chemical
and/or that may be relatively insoluble to the insult chemical.
Solubility (or insolubility) can be determined and/or estimated by
comparing the solubility parameter of a component (e.g., a polymer)
with that of an insult chemical's. If they are sufficiently
different, then a non-flame retardant chemical barrier film
comprising the component may function as a barrier since the insult
chemical is not soluble in the barrier film and may not migrate
through it. In some embodiments, the non-flame retardant chemical
barrier film has at least one layer that has at least one
difference in solubility parameter that is about 3.0 (calories per
cm.sup.3).sup.1/2 or greater, such as, for example, about 3, 3.5,
4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5,
12, 12.5. 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18,
18.5, 19, 19.5, 20 (calories per cm.sup.3).sup.1/2, or greater for
a chemical, such as, e.g., a chemical is listed in ASTM F23
F1001.
[0055] If a non-flame retardant chemical barrier film functions to
block the migration of an insult chemical, then this may be
attributed to the polymer film with the greatest difference in
solubility parameter from the insult. For example, a polymer film
of EVOH may be responsible for blocking the migration of acetone
since the difference in solubility parameter between EVOH and
acetone is 3.1 (calories per cm.sup.3).sup.1/2 while the difference
in solubility parameter between PE and acetone is only 1.9
(calories per cm.sup.3).sup.1/2. Thus. PE has a smaller difference
in solubility parameter compared to EVOH and may not function as
well as a barrier film against acetone compared to an EVOH barrier
film.
[0056] In some embodiments, the non-flame retardant chemical
barrier film is not physically and/or chemically disrupted by the
insult chemical and/or the non-flame retardant chemical barrier
film exhibits slow or no diffusion of the insult chemical through
the non-flame retardant chemical barrier film.
[0057] Referring again to FIG. 1, the second layer 20 comprising a
non-flame retardant chemical barrier film may be adhered to the
third layer 30 of the composite 100 with an adhesive (e.g., a flame
retardant adhesive). In some embodiments, no adhesive is used to
adhere the second layer 20 to the third layer 30. In some
embodiments, the third layer 30 is a polymeric coating (optionally
a flame retardant coating) that is applied onto the second layer 20
with no adhesive between so that a surface of the second layer 20
directly contacts a surface of the third layer 30. The polymeric
coating (optionally a flame retardant coating) may form a film
(e.g., a polymeric film), in some embodiments, the third layer 30
may comprise a polymeric film (optionally a flame retardant film).
In some embodiments, the third layer 30 may be and/or comprise an
outer layer, such as, e.g., an outer flame and/or splash barrier
layer.
[0058] A third layer and/or outer layer of a composite of the
present invention may have at least some degree of flame resistance
and/or chemical resistance. In some embodiments, the third layer in
a composite of the present invention may comprise a fire retardant
additive. In some embodiments, the third layer does not comprise a
fire retardant additive.
[0059] Example polymers that may be present in the third layer
include, but are not limited to, polyvinylidene chloride,
chlorinated polyethylene (CPE), PVC, ethyl methyl acrylate (EMA),
acrylic polymers, acrylonitrile rubber, poly(ester urethanes)
(PEU), PEEK, polyethylene, polyolefin, ECTFE, PVF, nylon, EVA,
EVOH, polypropylene, polyester, and/or EVCL. In some embodiments,
the third layer of a composite of the present invention may
comprise a halogenated polymer, such as, for example, polyvinyl
chloride, polyvinyl bromide, polyvinyl fluoride, and/or
polyvinylidene chloride (PVDC). In some embodiments, the third
layer may not comprise inherently flame resistant polymers, but may
be rendered flame resistant by the application of sufficient fire
retardant additives within the film itself and/or within the flame
retardant adhesive binding the third layer to the non-flame
retardant chemical barrier polymeric film, thereby effectively
rendering the third layer flame retardant. In some embodiments, the
third layer may comprise polyvinyl chloride. In some embodiments, a
composite of the present invention does not comprise polyvinyl
fluoride or butyl rubber.
[0060] In some embodiments, the third layer comprises a polymer
selected from PEEK, polyethylene, polyolefin, ECTFE, PVF, nylon,
EVA, EVOH, polypropylene, polyester, EVCL, and/or PVC, and
optionally comprises a flame retardant additive. In some
embodiments, the third layer is applied a polymeric coating that
comprises polyvinylidene chloride, chlorinated polyethylene (CPE),
PVC, ethyl methyl acrylate (EMA), acrylic polymers, acrylonitrile
rubber, and/or poly(ester urethanes) (PEU), and optionally
comprises a flame retardant additive. A polymeric coating may be
applied according to methods known to those of skill in the art. In
some embodiments, the polymeric coating may be hot melt extruded
onto the second layer and the polymeric coating may comprise, for
example, PVDC, CPE, PVC, and/or FR filled EMA. In some embodiments,
the polymeric coating may be applied as fluid (e.g., an aqueous
liquid) onto the second layer that is subsequently dried and cured,
and the polymeric coating may comprise, for example, PVDC, CPE, FR
filled acrylic, FR filled acylonitrile rubber, and/or FR filled
PEU.
[0061] The weight and type of the polymeric film of the third layer
may be selected to be complementary to the non-flame retardant
chemical barrier polymeric film in order to achieve the desired
properties for the overall composite. In some embodiments, the
third layer of a composite of the present invention may have a
thickness in a range of about 0.0001 inches to about 0.008 inches.
In some embodiments, the third layer of a composite of the present
invention may have a thickness in a range of about 0.2 mils (1
mil=0.001 inches) to about 6.0 mils. The thickness of the third
layer may depend on the end use, and may be optimized to control
the composite's strength, abrasion resistance, and/or barrier
properties for an intended end use while being cost effective. The
third layer of a composite of the present invention may have a
basis weight in a range of about 0.05 osy to about 10 osy, such as,
for example, about 0.15 osy to about 5 osy or about 1 osy to about
4 osy. In some embodiments, the third layer may have a basis weight
of about 0.05, 0.1, 0.25. 0.5, 0.75, 1, 1.5, 2, 2.5, 3, 3.5, 4,
4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 osy. In some
embodiments, the third layer a composite of the present invention
may make up about 8% to about 50% by weight of the composite, such
as, for example, about 15% to about 50% or about 20% to about
45%.
[0062] An adhesive (e.g., a flame retardant adhesive) may be used
to bind and/or adhere the first layer and second layer and/or the
second layer and third layer of a composite of the present
invention. In some embodiments, the adhesive may be a flame
retardant and/or flame resistant adhesive. In some embodiments, the
nonwoven fabric of the first layer may be bonded and/or adhered to
the non-flame retardant chemical barrier film of the second layer
using an adhesive (e.g., a flame retardant adhesive), which may be
applied to a surface of the nonwoven fabric and/or to a surface of
the non-flame retardant chemical barrier film. In some embodiments,
the adhesive used to bond and/or adhere the non-flame retardant
chemical barrier film of the second layer to the first layer is not
a flame retardant adhesive, and optionally the non-flame retardant
adhesive may be applied onto a surface of the nonwoven fabric
and/or onto a surface of the non-flame retardant chemical barrier
film in a discontinuous pattern so that a discontinuous adhesive
layer is formed between the first layer and second layer. The
non-flame retardant chemical barrier film may be bonded and/or
adhered to the polymeric film of the third layer using a flame
retardant adhesive, which may be applied to a surface of the flame
retardant film and/or to a surface of the non-flame retardant
chemical barrier film. The adhesive used between the first and
second layers and the second and third layers may be the same or
may be different. In some embodiments, the adhesive between the
first and second layers and the second and third layers may be a
flame retardant adhesive that comprises the same fire retardant
additive. In some embodiments, the adhesive used to bond and/or
adhere the first layer and the second layer together is a non-flame
retardant adhesive and no adhesive is used to bond and/or adhere
the second and third layers. In some embodiments, the adhesive used
to bond and/or adhere the first layer and the second layer is a
non-flame retardant adhesive and the adhesive used to bond and/or
adhere the second layer and the third layer together is a flame
retardant adhesive. In some embodiments, the adhesive may comprise
EVA, acrylic (e.g., an elastomeric acrylic), acrylonitrile rubber,
poly(vinyl acetate), polyvinyl alcohol, polyester, APAO, PVC,
and/or PVDC, and optionally a flame retardant.
[0063] A flame retardant adhesive may comprise an adhesive. The
term "adhesive" as used herein refers to any binder and/or chemical
substance that can hold two layers together and/or cause them to
stick together with a measurable force. For example, an adhesive
may bond a film to another film that may comprise the same or a
different material. Alternatively or in addition, an adhesive may
bond a film to a fabric.
[0064] In some embodiments, the adhesive may be an aqueous,
solvent, hot melt, thermoplastic or thermoset adhesive. Example
adhesives that may be used include, but are not limited to,
pressure sensitives, polyesters, acrylates, acetates, polyamides,
ethylene vinyl acetates (EVAs), ethyl methacrylates (EMAs),
polyolefins, thermoplastic polyurethanes, and/or reactive moisture
cure urethanes. In some embodiments, the adhesive provides greater
than 15 grams of peel strength between the contiguous layers when
tested in accordance with ASTM 5170. The adhesive may be inherently
flame retardant or may contain an additive that causes the adhesive
to be flame retardant and maintain its adhesive properties.
[0065] In some embodiments, a flame retardant adhesive may comprise
a halogenated flame retardant compound, such as, e.g., an additive
and/or binder. A halogenated flame retardant may be combined with
various antimony, zinc, and/or aluminate synergists. A halogenated
adhesive may be very efficient at extinguishing flames and
preventing the spread of flames. However, many halogenated flame
retardants have come under regulatory scrutiny. In some
embodiments, an adhesive and/or flame retardant may be
environmentally friendly. In some embodiments, an aqueous adhesive
compound may be used that comprises an acrylic binder, Type II
Ammonium Poly Phosphate (APP) or melamine encapsulated APP, and
particles of low melt polyester adhesive powder. In some
embodiments, a flame retardant adhesive may be foam coated onto the
nonwoven fabric and dried, and optionally subsequently it may be
reheated to activate the adhesive (e.g., adhesive particles) and
pressed against the polymeric film of the second layer to laminate
the layers together. Example classes of adhesives that may be used
in a composite of the present invention include, but are not
limited to, those that comprise a halogen, phosphate, nitrogen,
expanded and/or expandable graphite, and/or inorganic materials
such as, e.g., aluminum trihydrate (ATH), clays, and/or other
minerals.
[0066] Any suitable amount of flame retardant may be added to an
adhesive. In some embodiments, the dry add on for the flame
retardant adhesive is in a range of about 0.1 osy to about 1.5 osy
per layer of the composite. The concentration of the flame
retardant in the flame retardant adhesive may depend on the type of
flame retardant included, in some embodiments, a flame retardant
may be present in the flame retardant adhesive in an amount of
about 25% to about 80% by weight of the flame retardant adhesive,
such as, for example, about 30% to about 70%, about 50% to about
75%, about 55% to about 70%, or about 40% to about 55% by weight of
the flame retardant adhesive. In some embodiments, a flame
retardant may be present in the flame retardant adhesive in an
amount of about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%,
75%, or 80%. In some embodiments, a flame retardant adhesive may
comprise a flame retardant, such as, for example Apexical
Flameproof P1F-024, in an amount of about 40% by weight of the
flame retardant adhesive.
[0067] An adhesive (e.g., a flame retardant adhesive) may be
applied to a surface in a manner to provide a pattern or randomly.
Some embodiments include that when an adhesive is applied to a
surface an adhesive layer may be applied and/or formed. The
adhesive layer may be substantially continuous or may be
discontinuous and may cover at least about 1% and up to 100% of the
surface as measured using microscopic examination of the coated
surface. In some embodiments, an adhesive layer may be provided on
a surface and the adhesive layer may cover at least about 2%, 5%,
10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or more of the
surface. One or more layers of an adhesive (e.g., a flame retardant
adhesive) (e.g., 1, 2, 3, 4, 5, or more) may be applied to a
surface, which may provide one or more adhesive layers (e.g., 1, 2,
3, 4, 5, or more). In some embodiments, the adhesive may be a flame
retardant and/or flame resistant adhesive and may form a layer
(e.g. a continuous layer) on a surface of the second layer (e.g.,
between second layer and third layer) that excludes the non-flame
retardant barrier film from oxygen. In some embodiments, after
applying an adhesive to a surface (e.g., a surface of one of the
layers of the composite), the layers of the composite may be
pressed together, which may cause them to stick to each other
and/or stay in intimate contact. The process of joining two layers
with an adhesive is referred to herein as "adhesive
lamination".
[0068] An adhesive (e.g., a flame retardant adhesive) may be
applied to a surface using methods known to those of skill in the
art. For example, an adhesive may be applied using gravure printing
(e.g., aqueous or solvent base media), screen printing, knife over
roll coating, spraying, transfer printing, adhesive web, gravure
printing hot melt adhesive (e.g., thermoplastic polymer based
pressure sensitive adhesive (PSA) or reactive thermoset based,
e.g., moisture cure urethane), porous coat hot melt adhesive (e.g.,
thermoplastic polymer based PSA or reactive thermoset based, e.g.,
moisture cure urethane), slot coating (thermoplastic polymer based
PSA or reactive thermoset based, e.g., moisture cure urethane),
and/or powder sprinkling (via Schindler roll).
[0069] In some embodiments, an adhesive (e.g., a flame retardant
adhesive) in a composite of the present invention may have a basis
weight in a range of about 0.01 osy to about 2 osy, such as, for
example, about 0.05 osy to about 1 osy or about 0.1 osy to about
0.75 osy. In some embodiments, the adhesive may have a basis weight
of about 0.05, 0.1, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, or 2 osy.
In some embodiments, the adhesive in a composite of the present
invention may make up about 1% to about 25% by weight of the
composite, such as, for example, about 1% to about 20% or about 5%
to about 15% by weight of the composite.
[0070] In some embodiments, the non-flame retardant barrier film,
which may be the second layer in a composite of the present
invention, and/or the polymeric film (e.g., a flame retardant outer
film), which may be the third layer in a composite of the present
invention, may be surface modified to improve interaction with one
or more adhesive layers and/or coatings. The surface modification
may include processes such as, but not limited to, etching,
embossing, plasma treatment, flame treatment and/or corona
treatment. The surface modification may be an additional coating or
a co-extruded tie layer on one or more surfaces to facilitate
bonding to the film. For example, a surface of the non-flame
retardant barrier film making up the second layer of a composite of
the present invention and/or the polymeric film making up the third
layer of the composite may comprise, e.g., adhesive polymers and/or
additives such as ethylene vinyl acetate (EVA), maleic anhydride
modified polymers, methyl methacrylate containing polymer blends
and/or other ingredients known to those skilled in the art of film
manufacturing.
[0071] In some embodiments, the first layer of a composite of the
present invention may be a flame retardant fabric that may contact
a user's skin and/or clothing and may be adhered to the second
layer using one or more layers of adhesive (e.g., a flame retardant
adhesive). The adhesive(s) (e.g., a flame retardant adhesive(s)),
the second layer, and/or the third layer may have several
distinguishing properties, which may allow the resulting composite
to fulfill the intended purpose of a garment. For example, flame
retardant properties, chemical permeation resistance, surface
abrasion resistance, visual appearance, esthetic properties, and/or
other characteristics known to those trained in the art may be
incorporated into the composite through the intelligent selection
of raw materials. In some embodiments, the nonwoven fabric may
comprise at least one layer of flame-resistant fibers such as,
e.g., Nomex, Kevlar, Kynol or Basofil fibers, which may be
commercially available at 1.25 ounces per square yard fabric
weight.
[0072] In some embodiments, a composite of the present invention
may be a laminate. The laminate may comprise a first layer of a
nonwoven fabric (e.g., a nonwoven fabric containing cellulose
fibers and synthetic fibers) having a fire retardant additive
applied thereto; a second layer of a non-flame retardant chemical
barrier polymeric film adhered to the first layer using a first
flame retardant adhesive; and a third layer that comprises a
polymeric film and is adhered to the second layer using a second
flame retardant adhesive. In some embodiments, the fire retardant
additive is applied to at least one surface of the nonwoven
fabric.
[0073] In some embodiments, the laminate may comprise a first layer
of a nonwoven fabric (e.g., a nonwoven fabric containing cellulose
fibers and synthetic fibers) having a fire retardant additive
applied thereto; a second layer of a non-flame retardant chemical
barrier polymeric film adhered to the first layer using a first
adhesive; and a third layer that comprises a polymeric film and is
adhered to the second layer using a second adhesive. In some
embodiments, the fire retardant additive is applied to at least one
surface of the nonwoven fabric. In some embodiments, the first
adhesive is not flame retardant and the second adhesive is a flame
retardant adhesive.
[0074] In some embodiments, the laminate may comprise a first layer
of a nonwoven fabric (e.g., a nonwoven fabric containing cellulose
fibers and synthetic fibers) having a fire retardant additive
applied thereto; a second layer of a non-flame retardant chemical
barrier polymeric film adhered to the first layer using a first
adhesive; and a third layer that comprises a polymeric film,
wherein no adhesive is used to adhere the third layer to the second
layer. In some embodiments, the fire retardant additive is applied
to at least one surface of the nonwoven fabric. In some
embodiments, the first adhesive is a flame retardant adhesive. In
some embodiments, the third layer is adhered to the second layer by
applying a polymeric coating directly onto a surface of the third
layer and the polymeric coating forms the polymeric film. In some
embodiments, the polymeric film comprises a flame retardant.
[0075] In some embodiments, the laminate may comprise a first layer
of a nonwoven fabric (e.g., a nonwoven fabric containing cellulose
fibers and synthetic fibers) having a fire retardant additive
applied thereto; a second layer of a non-flame retardant chemical
barrier polymeric film adhered to the first layer using a flame
retardant adhesive; and a third layer that comprises a flame
retardant abrasion resistant coating that has been applied to the
non-flame retardant chemical barrier polymeric film. In some
embodiments, the fire retardant additive is applied to at least one
surface of the nonwoven fabric.
[0076] In some embodiments, a composite of the present invention is
flame retardant and/or resistant to chemical penetration and/or
chemical permeation. In some embodiments, the composite is flame
retardant and resistant to both chemical penetration and chemical
permeation.
[0077] The composite may prevent chemical permeation at or below
threshold levels, such as, for example, those as cited in EN 14325
and/or ASTM F23 F739 chemical permeation test(s) when challenged
with one or more chemicals (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or
more) on the ASTM F23 F1001 list. In some embodiments, the
composite may prevent chemical permeation at or below threshold
levels, such as, for example, those as cited in EN 14325 and/or
ASTM F23 F739 chemical permeation test(s) when challenged with each
of the chemicals on the ASTM F23 F1001 list. Alternatively or in
addition, the composite may pass the NFPA 701-20.15 Method 1 open
flame vertical flammability test.
[0078] In some embodiments, a composite of the present invention
may have a burn behavior that is self-extinguishing and chat
forming with residual integrity and minor weight loss. This type of
burn behavior may translate into no contribution to excess body
burn as described in NFPA 2113 A.5.1.7 and 8. In these tests, a
primary garment meeting NFPA 2112 flash over protection is used as
the undergarment and the secondary garment comprises a composite of
the present invention which is over the primary garment. In
contrast, results of the NFPA 701 2015 Method 1 Flammability Test
such as: perpetual after-flame, melting away from flame
(thermoplastic material behavior), excessive mass loss of specimen,
and burning melted drips tend to translate into a non-compliant
over-garment or accessory by NFPA 2113 definition when worn over
the primary NFPA 21.12 garment (subjected to the NFPA 2112 thermal
manikin test). A secondary garment of the present invention that
comprises a composite of the present invention may not exhibit
perpetual after-flame, melting away from flame (thermoplastic
material behavior), excessive mass loss of specimen, and/or burning
melted drips when provided and/or worn over a primary NFPA 2112
garment and subjected to the NFPA 2112 thermal manikin test. It is
noted that a thermoplastic material often perpetuates an after
flame once the burner insult is over in a thermal manikin test and
will sustain an after-flame due to wicking of the melted garment
resulting in an increased body burn percentage. In contrast, it was
surprisingly discovered that a NFPA 2112 garment covered with a
composite and/or garment of the present invention self-extinguishes
and goes to a charred solid state. Thus, a composite and/or garment
of the present invention may be flame resistant in a
self-extinguishing behavior and may form a chat upon open flame
insult. Polymers that melt and flow can cause burn injuries and
also help to propagate flames. NFPA 701-1989 small scale;
NFPA701-2015 M1, as well as ASTM D13 D6413 Textile Vertical
Flammability "Method" are useful for determining if materials will
char or melt and flow.
[0079] In some embodiments, a composite and/or garment of the
present invention may have a weight loss of less than about 40%,
such as, for example, less than about 35%, 30%, 25%, 20%, 15%, 10%,
or 5%, when tested in accordance with NFPA 701-2015 Method 1. In
some embodiments, a composite and/or garment of the present
invention may have a weight loss in a range of about 1% to about
20%, such as, for example, about 1% to about 15%, when tested in
accordance with NFPA 701-2015 Method 1.
[0080] Further, it was surprisingly discovered that a composite
and/or garment of the present invention may provide chemical
penetration and/or chemical permeation resistance and may be
compliant to NFPA 2113 requirements. In contrast, commercially
available products, such as those at comparable weights to those of
the composite and/or garment of the present invention, are
non-compliant to NFPA 2113 requirements and may not exhibit good
flame resistance. Higher resistance to chemicals, whether gas,
liquid or particulate will benefit products designed to pass ASTM
F23 F739 (domestic) and EN 14325/ISO 6529-international criteria.
The composite and/or garment of the present invention may combine
improved chemical resistance and flame resistance into a single
light weight composite for use in PPE garments meeting NFPA 2113
and other criteria such as, e.g., NFPA 1991.
[0081] A composite and/or garment of the present invention may
provide increased or improved flame resistance and/or chemical
protection at a reduced material cost per unit compared to existing
flame resistant and/or chemical protective garments, such as, for
example, DuPont's ChemMAX3. In some embodiments, a composite of the
present invention may be used as an outer garment, such as, for
example, as a garment that is used, worn, and/or provided over a
primary NFPA 2112 garment. The composite may prevent and/or reduce
soiling and/or contamination of a primary garment (e.g., a NFPA
2112 primary garment). In some embodiments, when a composite and/or
garment of the present invention is exposed as a coverall on top of
a manikin fitted with a primary NFPA 2112 ensemble per thermal
manikin testing, the percent body burn result meets NFPA 2113
criteria as a compliant accessory.
[0082] In some embodiments, a composite and/or garment of the
present invention may allow for a reduction of PPE mass, which may
contribute to less wearer fatigue (vs. comparable PPE materials,
which can be bulky and/or heavier) and/or may provide improved
economics for targeted class provided protection. In some
embodiments, a composite and/or garment of the present invention
may be light weight. A composite of the present invention may have
sufficient structural integrity to fabricate a garment, such as,
for example, a PPE and/or protective apparel.
[0083] In some embodiments, a composite of the present invention
may be used to make and/or prepare a garment, such as, for example,
a chemically impervious garment. Any suitable method known to those
of skill in the art for making garments (e.g., for making
chemically impervious garments) using a composite can be used to
prepare a garment of the present invention. In some embodiments, a
garment of the present invention, which may be prepared using a
composite of the present invention, may be useful in applications
where PPE must meet NFPA standards. "Garment" as used herein refers
to a garment comprising a composite of the present invention. The
term "garment" includes any type of protective material and/or
device for a user (e.g., an animal (e.g., human), a machine or
equipment) and includes, but is not limited to, clothing (e.g.,
coveralls, suits, gloves, jackets, trousers, etc.), headgear,
shoes, blankets (e.g., wrap around blankets), covers, and the
like.
[0084] In some embodiments, a garment and/or composite of the
present invention may be used for and/or in a personal protection
ensemble (PPE). The garment and/or composite may be chemical
permeation resistant to liquids, solid particles, and/or gases
within the scope of the ASTM F23 F739 Chemical Permeation US
Domestic test, and International ISO 6529 Chemical Permeation test.
In some embodiments, a garment and/or composite of the present
invention (i.e., a garment comprising a composite of the present
invention) may be used over a NFPA 2112 garment. The garment and/or
composite may augment the flame retardant protection of the NFPA
2112 garment. In some embodiments, the garment and/or composite may
provide chemical permeation and/or penetration resistance. In some
embodiments, a garment and/or composite of the present invention
may meet NFPA 2113 requirements, such as, for example, the garment
and/or composite may meet NFPA 2113 A.5.1.7 and 8 requirements when
used over and/or to cover a primary NFPA 2112 flashover protection
compliant garment or device.
[0085] According to NFPA 2113 requirements found in Section A.5.1.7
and 8, a secondary cover garment and/or composite of the present
invention may provide further splash and/or chemical protection
and/or primary flashover flame protection that meets NFPA 2112.
Costly primary PPE garments that are NFPA 2112 rated for flashover
protection must not be used while contaminated, and if contaminated
require costly cleaning and recertification. In some embodiments, a
garment and/or composite of the present invention may meet NFPA
2113 (Section A.5.1.7 and 8) criteria and may provide protection to
primary NFPA 2112 PPE and the end user from the penetration and/or
permeation of harmful chemicals and/or from flash over fires.
[0086] A garment and/or composite of the present invention may
provide significantly bet-ter chemical permeation resistance and
equivalent flash over fire protection, such as, for example,
compared to currently available garments in the same limited use
labeled garment category. Current PPE garments withstand 60 minutes
of chemical liquid penetration in accordance with ASTM F23 F903
test and F1001 liquid chemical list, whereas the materials of the
current invention withstand 480 minutes of penetration. In some
embodiments, a garment and/or composite of the present invention
may withstand at least 60, 90, 120, 150, 180, 210, 240, 270, 300,
330, 360, 390, 420, 450, 480, 510, 540, 570, 600 minutes of
chemical liquid penetration in accordance with ASTM F23 F903 test
and F1001 liquid chemical list. In some embodiments, a garment
and/or composite of the present invention may provide chemical
permeation protection for at least 60, 90, 120, 150, 180, 210, 240,
270, 300, 330, 360, 390, 420, 450, 480, 510, 540, 570, 600 minutes
of chemical permeation in accordance with ASTM F23 F903 test and
F1001 liquid chemical list.
[0087] A composite of the present invention may be useful for other
various levels of chemical protective garments needing flame
resistance, such as, e.g., those used in heavy industry (e.g.
welding, equipment manufacturing), hazardous chemical remediation,
general laboratory work, electrical utilities (rain-ware, fire
protection), the petrochemical industry, pesticide applications,
and/or painting. In some embodiments, a composite of the present
invention may be formed into a protective cover for machinery
and/or equipment. In some embodiments, regardless of the specific
end use, a composite of the present invention may be used by itself
or in conjunction with one or more additional protective
material(s).
[0088] For purposes of this invention, a composite of the present
invention may comprise either flame retardant or flame resistant
materials, or may comprise a combination of flame retardant and
flame resistant materials. For purposes of this invention, the use
of flame retardant and flame resistant materials may be varied
depending on the end use requirements of the composite. In some
embodiments, materials may be incorporated into a composite that
are neither flame resistant nor flame retardant as long as the
composite meets the requirements of the end use application and
passes the desired testing standards.
[0089] The present invention is explained in greater detail in the
following non-limiting Examples.
EXAMPLES
Example 1
[0090] A 2.5 mil PVC Film (outer barrier "Layer 3" material) is
bonded to an Isoflex Packaging film sample H6527.701, which is a 2
Mil Coextruded 7 layer Polyethylene/EVOH/Polyethylene film
(chemical barrier film, non-flame retardant (non-FR) "Layer 2"
material) using a flame-retardant (FR) pressure sensitive adhesive
(FR PSA) compound. Subsequently, this structure is bonded to PFG
Style 0084-78830 nonwoven fabric (Structural FR "Layer 1" material)
using a FR PSA coating. A diagram of the composite is shown, in
FIG. 5.
[0091] From the exterior to interior in reference to a user, the
composite is organized as follows: PVC Film/FR. Adhesive/Coextruded
Polyethylene-EVOH (7 layer)/FR Adhesive/FR Finished Wood Pulp
Polyester Nonwoven.
Description Structural FR "Layer 1" Material of the Laminated
Composite: PFG Style 0084-78830 Construction Details.
[0092] A phosphate fire retardant additive, sold as Spartan 880 FR,
is applied to a 2.13 osy Sontara Jacob Holm spunlace wood
pulp/polyester fabric. The fabric is then dried on a pin tenter.
The dry solids add-on of the Spartan 880 FR is about 27 percent by
weight of the fabric. This nonwoven fabric is known in the garment
industry as Precision Fabrics Softguard WRFR Spunlace 55%
Woodpulp/45% Polyester. The spunlace nonwoven fabric is treated
with a flame retardant and water repellant finish. This fabric is
used in the last step of the laminating process as the nonwoven
fabric for the Structural FR "Layer 1" material of resulting
laminated composite.
Description of Steps:
[0093] 1. An aqueous-based flame retardant pressure sensitive
adhesive (FR PSA) is applied to the H6527.701 2 mil Coex PE/EVOH/PE
film by a #3 Meyer Rod. The Co-ex film is mounted on a true flat
and level surface where the coating adhesive is applied by dragging
the aqueous based mixture in front of the Meyer Rod in a manner
that leaves the desired amount of wet material on the 2 mil Coex
film (about 0.5 to 1.0 oz./sq.yd, wet adhesive.) The wet adhesive
coated film is mounted on a drying frame, and is then dried in a
circulating air oven to create a pressure sensitive adhering
surface that bonds upon contact with the second layer film under
heat and pressure. [0094] 2. The prior-coated H6527.701 2 mil Coex
PE/EVOH/PE film ("Layer 2") is laid in a flat manner upon the 2.5
mil PVC film ("Layer 3"). [0095] 3. The two films are then
processed through a belt laminator. The bi-laminate film under the
laminator belts is under pressure and reaches a temperature of
about 160 to 180 degrees Fahrenheit (F) for 15 to 25 seconds to
produce a flat laminate with adequate adhesion for the next step.
[0096] 4. The Coex side of the resulting bi-laminate film composite
is then coated with the same FR PSA, and dried in a circulating air
oven to create a pressure sensitive adhering surface to be bonded
to the wood-pulp side of the 0084 nonwoven fabric. [0097] 5. The
prior coated and dried side of the bilaminate film is laid in a
flat manner upon the wood pulp side of the Style 0084 Soft-Guard
WRFR Nonwoven. [0098] 6. The composite laminate of step five is
then processed under the laminator belts at about 160 to 180 F for
15 to 25 seconds to produce a flat tri-laminate with adequate
adhesion.
Example 2
[0099] This composite employs the same materials as Example 1
above, but was carried out on commercial scale equipment. This
composite has been tested extensively and found to pass the
standards cited throughout this document which include NFPA 701
2015 Method 1, ASTM F23 F739 Permeation Test with F23 F1001 List of
Chemicals and ASTM F23 F903 Liquid Penetration and equivalent
European and world-wide standards. Table 1 provides the composition
details for the composite and a diagram of the composite is shown
in FIG. 5.
TABLE-US-00001 TABLE 1 Composition details for the composite. % by
weight +/- Basis weight/caliper Component 10% PFG Style (+/-10%)
2.5 mil PVC Film 34.6 30561-063000 2.43osy or 82.4 ("Layer
3"material) Presco GSM/0.002'' or .0508 mm Polymeric FR adhesive
5.1 Adhesive comprising a blocked 0.35 osy or 11.9 GSM solids (FR
PSA) isocyanate, defoamer, a low intimately bonded/ glass
transition point adhesive assume 0'' on interface binder, and a
dispersion of antimony trioxide and brominated flame retardants.
Polyethylene/EVOH 22.5 30564-063000 1.6osy or 54.3 GSM/ 7layer
Co-extruded Isoflex Packaging Inc. NON FR film ("Layer 2" material)
Polymeric FR adhesive 5.1 Adhesive comprising a blocked 0.35 osy or
11.9 GSM Solids (FR PSA) isocyanate, defoamer, a low intimately
bonded/ glass transition point adhesive assume 0'' on interface
binder, and a dispersion of antimony trioxide and brominated flame
retardants. Finished Wood pulp 18.0 0084-7883-061000 Finished 1.29
osy or entangled paper side Spunlace process Woodpulp
43.7GSM/~.002'' or or cellulosic layer of entangled paper side to
0.0508 mm Nonwoven Base adhesive - portion of "Layer 1" "Layer 1a"
material Finished Polyester 14.7 0084-7883-061000 Finished 1.06 osy
or 35.9 gsm/ Staple Fiber side of Spunlace process Polyester
~0.0055'' or 0.1397 mm Nonwoven base entangled Staple side to
inside "Layer 1b" material garment - portion of "Layer 1" Total:
100 PEG style 6493-54009-056000 6.89osy +/- 10% (Example 2, FIG. 5)
or 233.6GSM +/- 10%/ 0.012'' or .3048 mm +/- 10%
[0100] Description of Steps: [0101] 1. A pressure sensitive
adhesive (PSA) containing flame retardant (FR PSA) is applied at 45
to 60 Grams per Square Meter (1.33 to 1.77 osy) to a clear 2 mil
PE/EVOH/PE Coextruded film. The FR PSA is dried and then bonded to
a 2.5 mil PVC film (basis weight is around 81 to 85 grams per
square meter or 2.39 to 2.51 osy). The aqueous based adhesive
precursor of the PSA is applied by a rotogravure print process. The
adhesive is then dried in a radiant or circulating air oven to
create a pressure sensitive adhering surface that bonds upon
contact with the second film. The resulting mass of dry adhesive
add on is between approximately 10 to 13.6 grams per square meter
(0.29 to 0.40 osy). The marriage or bonding of the two film
components is further assisted by preheating the webs and conveying
them through heated nip rolls. The resulting bi-laminate then
proceeds to step two. [0102] 2. The "Layer 2" side of the resulting
bi-laminate film composite is coated with FR PSA and dried in a
circulating air oven to create a pressure sensitive adhering
surface that bonds upon contact with the wood-pulp side of the
aforementioned 0084 nonwoven fabric. The bonding of the bi-laminate
coated film precursor and the nonwoven substrate is improved by
nipping the layers together at about 120 to 190 degrees Fahrenheit.
[0103] 3. The resulting tri-laminate composite exhibits a basis
weight of approximately 233.6 grams per square meter (6.89 osy) and
is approximately 0.016 inches in thickness (0.4064 mm). The
tri-laminate from step 2 is then calendared to adjust the
properties of the laminated composite. The calendaring process
makes the fabric thinner, and reduces both the handle-o-meter
(reduces stiffness) and coefficient of friction. (reduces
roughness) of the laminated composite.
TABLE-US-00002 [0103] test Test Method unit average Example 2 test
data basis weight INDA/EDANA NWSP oz./sq.yd. 6.89 +/- 10% 130.1
caliper INDA/EDANA NWSP inches 0.012 +/- .001 120.1 Grab MD
INDA/EDANA NWSP lbs. 49 110.1 Grab XD INDA/EDANA NWSP lbs. 53 110.1
Mullenburst INDA/EDANA NWSP psi 53 030.1 Trap Tear MD INDA/EDANA
NWSP lbs. 12 100.2 Trap Tear XD INDA/EDANA NWSP lbs. 22 100.2 Bond
Strength MD 3'' .times. 7'' AATCC #136/ASTM D13 gr./'' 133 D2724
Bond Strength XD 3'' .times. 7'' AATCC #136/ASTM D13 gr./'' 142
D2724 Handleometer MD INDA/EDANA NWSP grams 62 4'' .times. 7''-20
mm gap 090.3 Handleometer XD INDA/EDANA NWSP grams 48 4'' .times.
7''-20 mm gap 090.3 Vertical flame test Char length MD 0.5 lb. NFPA
701 1989 smsc inches 6.5 weight (12 second flame) After Flame MD
NFPA 701 1989 smsc seconds 0 Burning drip MD NFPA 701 1989 smsc
seconds 0 % weight loss MD NFPA 701 1989 smsc % 8 Char Length XD
0.5 lb. NFPA 701 1989 smsc inches 6 weight (12 second flame) After
Flame XD NFPA 701 1989 smsc seconds 0 Burning Drip XD NFPA 701 1989
smsc seconds 0 % weight loss XD NFPA 701 1989 smsc % 8 % weight
Loss MD NFPA 701 2015 Method 1 % loss 12 (45 second flame)
Overview of Examples 3-6
[0104] Examples 1 and 2 illustrate the construction method for
example composites of the present invention. Subsequent examples
illustrate possible film layer substitutions and/or additions to
further improve the chemical permeation resistance of
composites.
[0105] Many variations of the composites may be derived, such as,
for example, by adding film layers to a composite or by
substituting films for either layer 2, layer 3, or for both layers.
Halar@ 500LC and Tedlar.RTM. TCC15BL3 may be advantageous films for
achieving a high level of chemical permeation resistance.
Example 3
[0106] The composite of Example 3 is a variation of the composite
described in Example 1, except that new films are substituted for
both "Layer 2" and "Layer 3" of the composite. A 3 layer, 3 mil,
coex polyolefin blend PP/EVOH/PE film is substituted for the 7
layer coex film in Example 1, and a High Molecular Weight PVC film
is substituted for the regular PVC film in Example 1. These changes
reduce the permeation rate of Diethylamine, Tetrahydrofuran, and
gaseous 99% HCl to less than 0.1 micrograms breakthrough threshold
for the 480 minute test duration.
Example 4
[0107] The composite of Example 4 is constructed in the same manner
as the composite described in Example 3 with the exception of the
outer barrier "Layer 3" being a monolithic 2-mil PVF film (Tedlar
TCC15BL3). The composite of Example 4 achieved less than the 0.1
microgram threshold after a 480 minute insult from methanol per
ASTM F739 guidelines/ASTM F1001. While not wishing to be bound to
any particular theory, this added attribute is believed to be the
result of the outer "Layer 3" barrier substitution in the basic
composite design from Example 3.
Example 5
[0108] The composite of Example 5 is the same as the composite
described in Example 3 except that a 25 micron PEEK
(Polyetheretherketone-APTIV) film was substituted for "Layer 2" of
the composite to improve the composite's resistance to methanol
permeation. The addition of this film kept the methanol permeation
below 0.1 micrograms in 480 minutes of insult.
Example 6
[0109] The composite of Example 6 is similar to the composites
described in Examples 3 and 5 except that a 50 micron ECTFE
(copolymer of ethylene and chlorotrifluoroethylene--"Halar 500LC")
is added to the composite or substituted for layer 2. This film
also enhanced the composite's resistance to methanol permeation to
below the 0.1 micrograms in 480 minutes of insult.
Example 7
[0110] Table 2 provides examples of barrier films that may be
incorporated into a composite of the present invention. Some of the
barrier films described in Table 2 are similar to or the same as
those described in the above examples.
[0111] The lamination processes used in the examples are not
intended to limit the processes that can be used for constructing a
composite of the present invention. For example, corona treatment
of webs, gravure coating, hot nipping, and hot calendaring were
utilized for scale up of composites of the present invention. For
purposes of this invention, a composite of the present invention
may be constructed by any process or combination of processes known
to those trained in the arts of paper manufacture, nonwovens
manufacture, fabric and/or film adhesive lamination or film
extrusion.
TABLE-US-00003 TABLE 2 Example barrier film layer descriptions.
Film Description Details Coex7 layer 2 mil PE/ 2 mil total
thickness; 7 total layers of EVOH film polyethylene (PE) and
polyethylene vinyl alcohol (EVOH), the layer structure being:
PE/EVOH/PE/EVOH/PE/EVOH/PE (Examples 1 & 2 middle barrier
"Layer 2") Coex 3 layer 3 mil 3 mil total thickness; 3 distinct
layers ~1 mil polyolefin polypropylene each, the layered film
structure being: (PP) blend/EVOH/PE film Polyolefin PP
blend/EVOH/PE (Examples 3 & 4 middle "Layer 2") Monolithic 2
mil PVF film (Tedlar .RTM. TCC15BL3) (Example 4 outer "Layer 3")
Coex 3 layer 2.5 mil 2.5 mil total thickness; 3 layers total, the
Polyolefin PP layer structure being: Polyolefin PP blend/EVOH/PE
film blend/EVOH/PE ("Layer 2") Coex 3 layer 2 mil 2 mil total
thickness; 3 layers, the layer PE/EVOH/PE structure being:
PE/EVOH/PE Copolymer copolymer film ("Layer 2") APTIV 1000-025GS
25.mu. Single layer of PEEK film PolyEtherEtherKetone (Example 5 -
"Layer 2") (PEEK) Halar .RTM. ECTFE 50.mu. Single layer of Halar
.RTM. film (Example 6 - "Layer 2")
TABLE-US-00004 TABLE 3 Difference of solubility parameter and
results from ASTM F739 testing. Absolute Absolute Value Value ASTM
F739 Test Liquid (Test (Test Greater Normalized Sol Liquid Liquid
Delta ASTM Breakthrough Permeation Parameter Sol Para - Sol Para -
Difference F23 time in min. rate Steady Chemical test Liquids
Units: 8.0 13.0 of Sol F739 (>0.1 .mu.Gr./ State Max F1001
("Permeant") (cal/cm.sup.3).sup.1/2 PPE Barrier layer (PE)) (EVOH)
Parameter Status cm.sup.2/min.) .mu.Gr./cm.sup.2/min. ACETONE 9.9
Coex7layer 2 mil 1.9 3.1 3.1 PASS >480 NONE PE/EVOH film
DETECTED ACETONITRILE 11.9 Coex7layer 2 mil 3.9 1.1 3.9 PASS
>480 NONE PE/EVOH film DETECTED CARBON DlSULFIDE 10 Coex7layer 2
mil 2 3 3 PASS >480 NONE PE/EVOH film DETECTED DICHLOROMETHANE
Coex7layer 2 mil 8 13 13 PASS >480 NONE PE/EVOH film DETECTED
DIETHYLAMINE (DEA) 8 Coex7layer 2 mil 0 5 5 FAIL 130 5.2 PE/EVOH
film DIETHYLAMINE (DEA) 8 Coex 3 layer 3 mil 0 5 5 PASS >480
NONE Polyolefin(PP)/ DETECTED EVOH/PE film DIETHYLAMINE (DEA) 8
Coex 3 layer 2.5 mil 0 5 5 FAIL 91 14.7 Polyolefin(PP)/EVOH/ PE
film DIETHYLAMINE (DEA) 8 Coex 3 layer 2 mil 0 5 5 PASS >480
NONE PE/EVOH/PE DETECTED copolymer film DIMETHYLFORMAMIDE 12.14
Coex7layer 2 mil 4.14 0.86 4.14 PASS >480 NONE (DMF) PE/EVOH
film DETECTED ETHYL ACETATE 9.1 Coex7layer 2 mil 1.1 3.9 3.9 PASS
>480 NONE PE/EVOH film DETECTED N-HEXANE 7.3 Coex7layer 2 mil
0.7 5.7 5.7 PASS >480 NONE PE/EVOH film DETECTED METHANOL 14.5
Coex7layer 2 mil 6.5 1.5 6.5 FAIL 25 1.65 PE/EVOH film METHANOL
14.5 Coex 3 layer 3 mil 6.5 1.5 6.5 FAIL 64 2.24
Polyolefin(PP)/EVOH/ PE film METHANOL 14.5 Coex 3 layer 2.5 mil 6.5
1.5 6.5 FAIL 79 3.74 Polyolefin/EVOH/PE film METHANOL 14.5 Coex 3
layer 2 mil 6.5 1.5 6.5 FAIL 63 3.49 PE/EVOH/PE copolymer film
METHANOL 14.5 Polyetheretherketone 6.5 1.5 6.5 PASS >480 NONE
(PEEK)25.mu. film DEFECTED METHANOL 14.5 Halar ECTFE 50.mu. film
6.5 1.5 6.5 PASS >480 NONE DETECTED METHANOL 14.5 Monolithic 2
mil PVF Not Not Not found PASS >480 NONE film ("Tedlar") found
found DETECTED NITROBENZENE 10 Coex7layer 2 mil 2 3 3 PASS >480
NONE PE/EVOH film DETECTED SODIUM HYDROXIDE Coex7layer 2 mil 8 13
13 PASS >480 NONE 50% PE/EVOH film DETECTED SULFURIC ACID
Coex7layer 2 mil 8 13 13 PASS >480 NONE 93.1% 66.degree.B
PE/EVOH film DETECTED TETRACHLOROETHYLENE 9.3 Coex7layer 2 mil 1.3
3.7 3.7 PASS >480 NONE (perc) PE/EVOH film DETECTED
TETRAHYDROFURAN 9.1 Coex7layer 2 mil 1.1 3.9 3.9 FAIL 13 2.51 (THF)
PE/EVOH film TETRAHYDROFURAN 9.1 Coex 3 layer 3 mil 1.1 3.9 3.9
PASS >480 NONE (THF) Polyolefin(PP)/ DETECTED EVOH/PE film
TETRAHYDROFURAN 9.1 Coex 3 layer 2.5 mil 1.1 3.9 3.9 PASS >480
NONE (THF) Polyolefin(PP)/EVOH/ DETECTED PE film TETRAHYDROFURAN
9.1 Coex 3 layer 2 mil 1.1 3.9 3.9 PASS >480 NONE (THF)
PE/EVOH/PE DETECTED copolymer film TOLUENE 8.9 Coex7layer 2 mil 0.9
4.1 4.1 PASS >480 NONE PE/EVOH film DETECTED 8 13 13 Chemical
test Gases 8 13 13 F1001 AMMONIA ANHYDROUS Coex7layer 2 mil 8 13 13
PASS >480 NONE PE/EVOH film DETECTED 1,3-BUTADIENE inhibited
Coex7layer 2 mil 8 13 13 PASS >480 NONE 99% PE/EVOH film
DETECTED CHLORINE 99.5% Coex7layer 2 mil 8 13 13 PASS >480 NONE
PE/EVOH film DETECTED ETHYLENE OXIDE 99.7% Coex7layer 2 mil 8 13 13
PASS >480 NONE PE/EVOH film DETECTED HYDROGEN CHLORIDE
Coex7layer 2 mil 8 13 13 FAIL 182 0.156 99% PE/EVOH film HYDROGEN
CHLORIDE Coex 3 layer 3 mil 8 13 13 PASS >480 NONE 99%
Polyolefin(PP)/ DETECTED EVOH/PE film HYDROGEN CHLORIDE Coex 3
layer 2.5 mil 8 13 13 PASS >480 NONE 99% Polyolefin(PP)/EVOH/
DETECTED PE film HYDROGEN CHLORIDE Coex 3 layer 2 mil 8 13 13 FAIL
310 1.61 99% PE/EVOH/PE copolymer film METHYL CHLORIDE 9.7
Coex7layer 2 mil 1.7 3.3 3.3 PASS >480 NONE 99.5% PE/EVOH film
DETECTED
Example 8
[0112] Additional example composites of the present invention
include, but are not limited to, the following.
Example Embodiment 8A
[0113] Layer 1: A 1-6 osy, 4-25 mils FR treated PET/woodpulp
(cellulose) spunlace fabric with a first sublayer comprising
polyester and a second sublayer comprising woodpulp or cellulose,
wherein a surface of the second sublayer is adhered to Layer 2
[0114] Adhesive 1 (bonds Layer 1 to Layer 2): A 0.25-1.5 osy,
0.01-3 mils FR PSA (elastomeric acrylic adhesive intimate
continuous coated layer)
[0115] Layer 2: A 1-3.5 osy, 0.5-5 mils polyethylene/EVOH co-ex
film (non-FR)
[0116] Adhesive 2 (bonds Layer 2 to Layer 3): A 0.25-1.5 osy,
0.01-3 mils FR PSA (elastomeric acrylic adhesive intimate
continuous coated layer)
[0117] Layer 3: A 1-6 osy, 0.2-6 mils PVC outer chemical barrier FR
film
Example Embodiment 8B
[0118] Layer 1: A 1-6 osy, 4-25 mils FR treated PET/woodpulp
(cellulose) spunlace fabric with a first sublayer comprising
polyester and a second sublayer comprising woodpulp or cellulose,
wherein a surface of the second sublayer is adhered to Layer 2
[0119] Adhesive 1 (bonds Layer 1 to Layer 2): A 0.03-0.8 osy
amorphous poly-alpha-olefin copolymer (APAO) PSA adhesive intimate
discontinuous coated layer
[0120] Layer 2: A 1.0-3.5 osy, 0.5-5.0 mil polyethylene/EVOH co-ex
film (non-FR)
[0121] Adhesive 2 (bonds Layer 2 to Layer 3): A 0.25-2.5 osy,
0.1-3.0 mil FR PSA (elastomeric acrylic adhesive intimate
continuous coated layer)
[0122] Layer 3: A 1.0-6.0 osy, 0.2-6.0 mil PVC outer chemical
barrier FR film
Example Embodiment 8C
[0123] Layer 1: A 1-6 osy, 4-25 mils FR treated PET/woodpulp
(cellulose) spunlace fabric with a first sublayer comprising
polyester and a second sublayer comprising woodpulp or cellulose,
wherein a surface of the second sublayer is adhered to Layer 2
[0124] Adhesive 1 (bonds Layer 1 to Layer 2): A 0.25-1.5 osy,
0.01-3.0 mil FR PSA (elastomeric acrylic adhesive intimate
continuous coated layer)
[0125] Layer 2: A 1.0-3.5 osy, 0.5-5.0 mil polyethylene/EVOH co-ex
film (non-FR)
[0126] Adhesive 2 (bonds Layer 2 to Layer 3): none
[0127] Layer 3: 1.0-6.0 osy, 0.2-6 mils intimate self-adhering
durable continuous outer chemical barrier coating comprising ethyl
methacrylic acid (FR filled, hot melt extruded)
Example Embodiment 8D
[0128] Layer 1: A 1-6 osy, 4-25 mils FR treated PET/woodpulp
(cellulose) spunlace fabric with a first sublayer comprising
polyester and a second sublayer comprising woodpulp or cellulose,
wherein a surface of the second sublayer is adhered to Layer 2
[0129] Adhesive 1 (bonds Layer 1 to Layer 2): A 0.25-1.5 osy FR PSA
(elastomeric acrylic adhesive intimate continuous coated layer)
[0130] Layer 2: A 1.0-3.5 osy, 0.5-5.0 mil polyethylene/EVOH co-ex
film (non-FR)
[0131] Adhesive 2 (bonds Layer 2 to Layer 3): none
[0132] Layer 3: 1.0-6.0 osy, 0.2-6 mils intimate self-adhering
durable continuous outer chemical barrier coating comprising PVDC
coating (applied wet/dried/cured)
[0133] The foregoing is illustrative of the present invention, and
is not to be construed as limiting thereof. The invention is
defined by the following claims, with equivalents of the claims to
be included therein. All publications, patent applications,
patents, patent publications, and other references cited herein are
incorporated by reference in their entireties for the teachings
relevant to the sentence and/or paragraph in which the reference is
presented.
* * * * *